Conditioning shampoo composition

ABSTRACT

Disclosed are aqueous conditioning shampoo compositions containing a surfactant component in a shampoo with a particulate insoluble, dispersed, non-volatile conditioning agent having a particle size range of less than about 0.15 microns, crystalline agent and a deposition polymer.

FIELD OF THE INVENTION

This invention relates to conditioning shampoo compositions containing asurfactant component in a shampoo with a particulate insoluble,dispersed, non-volatile conditioning agent having a defined particlesize range, suspending agent and a deposition polymer. The compositionsprovide improved hair conditioning performance, including improved wethair feel.

BACKGROUND OF THE INVENTION

Human hair becomes soiled due to its contact with the surroundingatmosphere and, to a greater extent, from sebum secreted by the head.The build-up of the sebum causes the hair to have a dirty feel and anunattractive appearance. The soiling of the hair necessitates it beingshampooed with frequent regularity.

Shampooing the hair cleans by removing excess soil and sebum. However,the shampooing process has disadvantages in that the hair is left in awet, tangled and generally unmanageable state. Shampooing can alsoresult in the hair becoming dry or "frizzy", and a loss of luster, dueto removal of natural oils or other hair moisturizing materials. Aftershampooing, the hair can also suffer from a loss of "softness" perceivedby the user upon drying. The hair can also suffer from increased levelsof static upon drying after shampooing. This can interfere with combingand can result in fly-away hair. A variety of approaches have beendeveloped to alleviate the after-shampoo problems. These range from theinclusion of hair conditioning aids in shampoos to post-shampooapplication of hair conditioners, i.e., hair rinses. Hair rinses aregenerally liquid in nature and must be applied in a separate stepfollowing the shampooing, left on the hair for a length of time, andrinsed with fresh water. This, of course, is time consuming and is notas convenient as shampoos containing both cleaning and hair conditioningingredients.

While a wide variety of shampoos have been disclosed which containconditioning aids, they have not been totally satisfactory for a varietyof reasons. Cationic conditioning agents are highly desirable for use inhair conditioning due to their abilities to control static, improve wetdetangling, and provide a silky wet hair feel to the user. One problemwhich has been encountered in shampoos relates to compatibility problemsbetween good cleaning anionic surfactants and the many conventionalcationic agents which historically have been used as conditioningagents. Efforts have been made to minimize adverse interaction throughthe use of alternate surfactants and improved cationic conditioningagents. Cationic surfactants which provide good overall conditioning inhair rinse products, in general, tend to complex with anionic cleaningsurfactants and provide poor conditioning in a shampoo context. Inparticular, the use of soluble cationic surfactants that form solubleionic complexes do not deposit well on the hair. Soluble cationicsurfactants that form insoluble ionic complexes deposit on the hair butdo not provide good hair conditioning benefits, and tend to cause thehair to have a dirty, coated feel. The use of insoluble cationicsurfactants, e.g., tricetyl methyl ammonium chloride, can provideexcellent anti-static benefits but do not otherwise provide good overallconditioning. Many cationic polymers tend to build up on the hair toresult in an undesirable, "unclean" coated feel. Cationic polymerstherefore, conventionally, are preferably used at limited levels tominimize this problem. This, however, can limit the overall conditioningbenefits that are obtained. Additionally, cationic conditioning agentscommonly do not provide optimal overall conditioning benefits,particularly in the area of "softness", especially when delivered as aningredient in a shampoo composition.

Materials which can provide increased softness are nonionic silicones.Silicones in shampoo compositions have been disclosed in a number ofdifferent publications. Such publications include U.S. Pat. No.2,826,551, Geen, issued Mar. 11, 1958; U.S. Pat. No. 3,964,500, Drakoff,issued Jun. 22, 1976; U.S. Pat. No. 4,364,837, Pader, issued Dec. 21,1982; and British Patent 849,433, Woolston, issued Sep. 28, 1960. Whilethese patents disclose silicone containing compositions, they also didnot provide a totally satisfactory product in that it was difficult tomaintain the silicone well dispersed and suspended in the product.Recently, stable, insoluble silicone-containing hair conditioningshampoo compositions have been described in U.S. Pat. No. 4,741,855,Grote and Russell, issued May 3, 1988 and U.S. Pat. No. 4,788,066,Bolich and Williams, issued Nov. 29, 1988. These shampoo compositionscan deliver excellent overall conditioning benefits to the hair whilemaintaining excellent cleaning performance, even with the use of anionicdetersive surfactants, for a wide variety of hair types.

More recently, improved conditioning shampoos were provided in U.S. Ser.No. 07/622,699, Robert L. Wells, filed Dec. 5, 1990, now abandoned, andits continuation application Ser. No. 07/778,765, filed Oct. 21, 1991,now abandoned, wherein shampoos containing anionic surfactant,dispersed, insoluble silicone, and certain relatively low ionic strengthcationic polymers (greater than about 0.4 meq./gm) were disclosed. Thesecompositions provide excellent hair cleaning conditioning to a widevariety of hair types, especially including improved conditioning tohair damaged by color treatments, bleaching, permanents, etc.

Japanese Patent Application, Laid Open No. 56-72095, Jun. 16, 1981,Hirota et al. (Kao Soap Corp.) also discloses shampoo containingcationic polymer and silicone conditioning agents. Still other patentpublications relating to shampoos with cationic agents and siliconeinclude EPO Application Publication 0 413 417, published Feb. 20, 1991,Hartnett et al.

Another approach to providing hair conditioning benefits to shampoocompositions has been to use materials which are oily to the touch.These materials provide improved luster and shine to the hair. Oilymaterials have also been combined with cationic materials in the shampooformulations. Japanese Patent Application Showa 53-35902, laid open Oct.6, 1979 (Showa 54-129135), N. Uchino (Lion Yushi Co.), discloses hairtreatment compositions containing cationic polymer, fatty acid salt, andat least 10% of an oily component for use before or after shampooing.Suitable oily components are hydrocarbons, higher alcohols, fatty acidesters, glycerides, and fatty acids. Japanese Patent Application62[1987]-327266, filed Dec. 25, 1987, published Jul. 4, 1989, laid openNo. HEI 1[1987]-168612, Horie et al., discloses detergent compositionscontaining cationic surfactant and/or cationic polymer, anionicsurfactant, and specific esters of the formula RCOOR' wherein R and R'are straight or branched chain alkyls.

In spite of these attempts to provide optimal combinations of cleaningability and hair conditioning, it remains desirable to provide furtherimproved hair conditioning shampoo compositions. For instance, itremains desirable to improve overall conditioning, and especially shineand luster, wet and dry combing, and dry hair feel, of hair treated withshampoo containing silicone and cationic material. For shampooscontaining oily materials in combination with cationic materials, itremains desirable to improve overall conditioning, especially wetcombing and detangling, dry combing, and dry hair feel. However merelyincreasing the level of one or both conditioning ingredients can resultin adverse effects such as greasy hair feel and loss of fullness. It isdesirable to improve conditioning without suffering from thesedrawbacks.

One attempt to do this is disclosed in EPO Patent Publication No. 0413416, published Feb. 20, 1991, Robbins et al., which discloses shampoocontaining aminosilicone, anionic surfactant, cationic surfactant, and ahydrocarbon component. These types of formulations would normally beexpected to result in either excessive buildup of aminosilicone on thehair, and consequently greasy hair feel and loss of fullness, or arelatively limited degree of improvement due to intentional use of verylow levels of aminosilicone to avoid such adverse effects. The cationicsurfactants would have limited ability to condition the hair due tointeraction with the anionic surfactant.

EPO Patent Application Publication No. 0 413 417, published Feb. 20,1991, discloses shampoo containing anionic surfactant, and conditioningagents such as insoluble silicone (preferably aminosilicone), cationicsurfactant, polyethylenes, paraffins, microcrystalline waxes, C₁₈ -C₃₆fatty acids or triglycerides, high fatty alcohol esters of high fattyacids, and beeswax. Another patent document which discloses shampoocompositions and a variety of conditioning agents is U.S. Pat. No.3,964,500, Drakoff, issued Jun. 22, 1976. This patent relates to shampoocontaining silicone conditioner and a hair bodying agent selected fromcertain wood rosins, shellac, sucrose acetate isobutyrate, and cationicamino cellulose.

A recent approach to providing hair conditioning benefits to shampoo isdescribed in U.S. Pat. No. 5,085,857 (Reid et al.). The compositiondisclosed combines a surfactant system (selected from anionic, nonionic,or amphoteric, or mixtures thereof), cationic guar derived polymer, andnonvolatile silicone having particle size less than 2 microns.

In spite of all these approaches and attempts to provide optimumcombinations of shampoos and hair conditioners, it remains desirable toprovide still improved conditioning shampoos. It has now been found thatimproved overall conditioning, especially wet conditioning, can beachieved by combining a surfactant component in a shampoo with aparticulate insoluble, dispersed, non-volatile conditioning agent havinga particle size range of less than about 0.15 microns, crystalline agentand a deposition polymer. These compositions can provide improvedconditioning while reducing the level of undesirable side effects thatcan result from increasing the level of conditioning agent in priorknown conditioning systems. As discussed previously, a conditioningagent system containing too much silicone can result in silicone buildup on the hair over repeated usages and to loss of fullness of the hair.Too much oil results in an oily feel and a loss of fullness of the hair.Too much cationic conditioning agent results in a coated, dirty feel ofthe hair. Now it has been found that the components of the presentinvention can provide improved overall conditioning while minimizing theadverse effects of conditioning agent build-up that otherwise can beincurred upon increasing the levels of individual components in priorknown conditioning systems.

It is an object of this invention to provide shampoo compositions, whichcan provide excellent cleaning performance and improved levels ofconditioning while minimizing any adverse side effects associated withbuild-up due to the use of excess conditioning agent.

It is also an object of this invention to provide a method for cleaningand conditioning the hair which can provide excellent cleaning incombination with improved conditioning, while minimizing adverse sideeffects associated with excess build-up of conditioning agent on thehair.

These objects will become apparent from the description which follows,as may other objects become apparent upon a reading of said description.

SUMMARY OF THE INVENTION

An aqueous shampoo composition comprising:

a) from about 5.0% to about 50% of a surfactant component,

b) a non-volatile conditioning component having a mean particle size ofless than about 0.15 microns;

c) from about 0.01% to about 3.0% of a deposition polymer;

d) from about 0.1% to about 5% of a crystalline agent; and

e) an aqueous carrier.

DETAILED DESCRIPTION OF THE INVENTION

The shampoo compositions of the present invention can comprise, consistof, or consist essentially of the essential elements and limitations ofthe invention described herein, as well any of the additional oroptional ingredients, components, or limitations described herein.

All percentages, parts and ratios are based upon the total weight of theshampoo compositions of the present invention, unless otherwisespecified. All such weights as they pertain to listed ingredients arebased on the active level and, therefore, do not include carriers orby-products that may be included in commercially available materials,unless otherwise specified.

As used herein, the term "soluble" refers to any material that issufficiently soluble in water to form a substantially clear solution tothe naked eye at a concentration of 0.1% by weight of the material inwater at 25° C. Conversely, the term "insoluble" refers to all othermaterials that are therefore not sufficiently soluble in water to form asubstantially clear solution to the naked eye at a concentration of 0.1%by weight of the other material in water at 25° C.

As used herein, the term "liquid" refers to any visibly (by the nakedeye) flowable fluid under ambient conditions (about 1 atmosphere ofpressure at about 25° C.)

The shampoo compositions of the present invention, including theessential and optional components thereof, are described in detailhereinafter.

Surfactant Component Detersive Surfactant

The shampoo compositions of the present invention comprise a detersivesurfactant suitable for use on hair or skin. Suitable surfactantsinclude anionic surfactants, nonionic surfactants, amphotericsurfactants, zwitterionic surfactants, or mixtures thereof. The purposeof the detersive surfactant is to provide cleansing performance to thecomposition. The term detersive surfactant, as used herein, is intendedto distinguish these surfactants from surfactants which are primarilyemulsifying surfactants, i.e. surfactants which provide an emulsifyingbenefit and which have low cleansing performance. It is recognized thatmost surfactants have both detersive and emulsifying properties. It isnot intended to exclude emulsifying surfactants from the presentinvention, provided the surfactant also possesses sufficient detersiveproperties to be useful herein.

Concentrations of the surfactant in the shampoo composition range fromabout 5% to about 50%, preferably from about 8% to about 30%, and morepreferably from about 10% to about 25%, by weight of the composition.

Anionic Surfactants

Anionic surfactants useful herein include alkyl and alkyl ethersulfates. These materials have the respective formulae ROSO₃ M and RO(C₂H₄ O) SO₃ M, wherein R is alkyl or alkenyl of from about 8 to about 30carbon atoms, x is 1 to about 10, and M is hydrogen or a cation such asammonium, alkanolammonium (e.g., triethanolammonium), a monovalent metalcation (e.g., sodium and potassium), or a polyvalent metal cation (e.g.,magnesium and calcium). Preferably, M should be chosen such that theanionic surfactant component is water soluble. The anionic surfactant orsurfactants should be chosen such that the Krafft temperature is about15° C. or less, preferably about 10° C. or less, and more preferablyabout 0° or less. It is also preferred that the anionic surfactant besoluble in the composition hereof.

Krafft temperature refers to the point at which solubility of an ionicsurfactant becomes determined by crystal lattice energy and heat ofhydration, and corresponds to a point at which solubility undergoes asharp, discontinuous increase with increasing temperature. Each type ofsurfactant will have its own characteristic Krafft temperature. Kraffttemperature for ionic surfactants is, in general, well known andunderstood in the art. See, for example, Myers, Drew, Surfactant Scienceand Technology, pp. 82-85, VCH Publishers, Inc. (New York, N.Y., USA),1988 (ISBN 0-89573-399-0), which is incorporated by reference herein inits entirety.

In the alkyl and alkyl ether sulfates described above, preferably R hasfrom about 12 to about 18 carbon atoms in both the alkyl and alkyl ethersulfates. The alkyl ether sulfates are typically made as condensationproducts of ethylene oxide and monohydric alcohols having from about 8to about 24 carbon atoms. The alcohols can be derived from fats, e.g.,coconut oil, palm oil, tallow, or the like, or the alcohols can besynthetic. Lauryl alcohol and straight chain alcohols derived fromcoconut oil and palm oil are preferred herein. Such alcohols are reactedwith 1 to about 10, and especially about 3, molar proportions ofethylene oxide and the resulting mixture of molecular species having,for example, an average of 3 moles of ethylene oxide per mole ofalcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates which can be used in thepresent invention are sodium and ammonium salts of coconut alkyltriethylene glycol ether sulfate; tallow alkyl triethylene glycol ethersulfate, and tallow alkyl hexaoxyethylene sulfate. Highly preferredalkyl ether sulfates are those comprising a mixture of individualcompounds, said mixture having an average alkyl chain length of fromabout 12 to about 16 carbon atoms and an average degree of ethoxylationof from 1 to about 4 moles of ethylene oxide. Such a mixture alsocomprises from 0% to about 20% by weight of C₁₂₋₁₃ compounds; from about60% to about 100% by weight of C₁₄₋₁₅₋₁₆ compounds, from 0% to about 20%by weight of C₁₇₋₁₈₋₁₉ compounds; from about 3% to about 30% by weightof compounds having a degree of ethoxylation of 0; from about 45% toabout 90% by weight of compounds having a degree of ethoxylation of from1 to about 4; from about 10% to about 25% by weight of compounds havinga degree of ethoxylation of from about 4 to about 8; and from about 0.1%to about 15% by weight of compounds having a degree of ethoxylationgreater than about 8.

Other suitable anionic surfactants are the water-soluble salts oforganic, sulfuric acid reaction products of the general formula [R₁ -SO₃-M] where R₁ is selected from the group consisting of a straight orbranched chain, saturated aliphatic hydrocarbon radical having fromabout 8 to about 24, preferably about 10 to about 18, carbon atoms; andM is as previously described above in this section. Examples of suchsurfactants are the salts of an organic sulfuric acid reaction productof a hydrocarbon of the methane series, including iso-, neo-, andn-paraffins, having about 8 to about 24 carbon atoms, preferably about12 to about 18 carbon atoms and a sulfonating agent, e.g., SO₃, H₂ SO₄,obtained according to known sulfonation methods, including bleaching andhydrolysis. Preferred are alkali metal and ammonium sulfonated C₁₀₋₁₈n-paraffins.

Still other suitable anionic surfactants are the reaction products offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide where, for example, the fatty acids are derived from coconutor palm oil; or sodium or potassium salts of fatty acid amides of methyltauride in which the fatty acids, for example, are derived from coconutoil. Other similar anionic surfactants are described in U.S. Pat. Nos.2,486,921, 2,486,922, and 2,396,278, which are incorporated by referenceherein in their entirety.

Other anionic surfactants suitable for use in the shampoo compositionsare the succinates, examples of which include disodiumN-octadecylsulfosuccinate; disodium lauryl sulfosuccinate; diammoniumlauryl sulfosuccinate; tetra sodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate; the diamyl ester ofsodium sulfosuccinic acid; the dihexyl ester of sodium sulfosuccinicacid; and the dioctyl ester of sodium sulfosuccinic acid.

Other anionic surfactants suitable for use in the shampoo compositionsare those that are derived from amino acids. Nonlimiting examples ofsuch surfactants include N-acyl-L-glutamate, N-acyl-N-methyl-β-alanate,N-acylsarcosinate, and their salts.

Still other useful surfactants are those that are derived from taurine,which is also known as 2-aminoethanesulfonic acid. An example of such anacid is N-acyl-N-methyl taurate.

Other suitable anionic surfactants include olefin sulfonates havingabout 10 to about 24 carbon atoms. The term "olefin sulfonates" is usedherein to mean compounds which can be produced by the sulfonation ofalpha-olefins by means of uncomplexed sulfur trioxide, followed byneutralization of the acid reaction mixture in conditions such that anysulfones which have been formed in the reaction are hydrolyzed to givethe corresponding hydroxy-alkanesulfonates. The sulfur trioxide can beliquid or gaseous, and is usually, but not necessarily, diluted by inertdiluents, for example by liquid SO₂, chlorinated hydrocarbons, etc.,when used in the liquid form, or by air, nitrogen, gaseous SO₂, etc.,when used in the gaseous form.

The alpha-olefins from which the olefin sulfonates are derived aremono-olefins having about 12 to about 24 carbon atoms, preferably about14 to about 16 carbon atoms. Preferably, they are straight chainolefins.

In addition to the true alkene sulfonates and a proportion ofhydroxy-alkanesulfonates, the olefin sulfonates can contain minoramounts of other materials, such as alkene disulfonates depending uponthe reaction conditions, proportion of reactants, the nature of thestarting olefins and impurities in the olefin stock and side reactionsduring the sulfonation process. A specific alpha-olefin sulfonatemixture of the above type is described more fully in U.S. Pat. No.3,332,880, to Pflaumer and Kessler, issued Jul. 25, 1967, which isincorporated by reference herein in its entirety.

Another class of anionic surfactants suitable for use in the shampoocompositions are the beta-alkyloxy alkane sulfonates. These compoundshave the following formula: ##STR1## where R¹ is a straight chain alkylgroup having from about 6 to about 20 carbon atoms, R² is a lower alkylgroup having from about 1, preferred, to about 3 carbon atoms, and M isas hereinbefore described. Many other anionic surfactants suitable foruse in the shampoo compositions are described in McCutcheon's,Emulsifiers and Detergents. 1989 Annual, published by M. C. PublishingCo., and in U.S. Pat. No. 3,929,678, which descriptions are incorporatedherein by reference in their entirety. Preferred anionic surfactants foruse in the shampoo compositions include ammonium lauryl sulfate,ammonium laureth sulfate, triethylamine lauryl sulfate, triethylaminelaureth sulfate, triethanolamine lauryl sulfate, triethanolamine laurethsulfate, monoethanolamine lauryl sulfate, monoethanolamine laurethsulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate,lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodiumlaureth sulfate, potassium lauryl sulfate, potassium laureth sulfate,sodium lauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine,cocoyl sarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate,sodium cocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,potassium lauryl sulfate, triethanolamine lauryl sulfate,triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate,monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate, andsodium dodecyl benzene sulfonate, sodium N-lauroyl-L-glutamate,triethanol N-lauryoyl-L-glutamate, sodium N-lauroyl-N-methyl taurate,sodium N-lauroyl-N-methyl-β-aminopropionate, and mixtures thereof.

Amphoteric and Zwitterionic Surfactants

The shampoo compositions can comprise amphoteric and/or zwitterionicsurfactants. Amphoteric surfactants suitable for use in the shampoocompositions include the derivatives of aliphatic secondary and tertiaryamines in which the aliphatic radical is straight or branched and one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic water solubilizing group, e.g.,carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Zwitterionic surfactants suitable for use in the shampoo compositionsinclude the derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals are straight orbranched, and wherein one of the aliphatic substituents contains fromabout 8 to about 18 carbon atoms and one contains an anionic group,e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A generalformula for these compounds is: ##STR2## where R² contains an alkyl,alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbonatoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1glyceryl moiety; Y is selected from the group consisting of nitrogen,phosphorus, and sulfur atoms; R³ is an alkyl or monohydroxyalkyl groupcontaining 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom,and 2 when Y is a nitrogen or phosphorus atom; R⁴ is an alkylene orhydroxyalkylene of from 1 to about 4 carbon atoms and Z is a radicalselected from the group consisting of carboxylate, sulfonate, sulfate,phosphonate, and phosphate groups.

Examples of amphoteric and zwitterionic surfactants also includesultaines and amidosultaines. Sultaines, including amidosultaines,include for example, cocodimethylpropylsultaine,stearyldimethylpropylsultaine, lauryl-bis-(2-hydroxyethyl)propylsultaine and the like; and the amidosultaines such ascocamidodimethylpropylsultaine, stearylamidododimethylpropylsultaine,laurylamidobis-(2-hydroxyethyl) propylsultaine, and the like. Preferredare amidohydroxysultaines such as the C₁₂ -C₁₈ hydrocarbyl amidopropylhydroxysultaines, especially C₁₂ -C₁₄ hydrocarbyl amido propylhydroxysultaines, e.g., laurylamidopropyl hydroxysultaine andcocamidopropyl hydroxysultaine. Other sultaines are described in U.S.Pat. No. 3,950,417, which is incorporated herein by reference in itsentirety.

Other suitable amphoteric surfactants are the aminoalkanoates of theformula R--NH(CH₂)_(n) COOM, the iminodialkanoates of the formulaR--N[(CH₂)_(m) COOM]₂ and mixtures thereof, wherein n and m are numbersfrom 1 to about 4, R is C₈ -C₂₂ alkyl or alkenyl, and M is hydrogen,alkali metal, alkaline earth metal, ammonium or alkanolammonium.

Examples of suitable aminoalkanoates include n-alkylamino-propionatesand n-alkyliminodipropionates, specific examples of which includeN-lauryl-beta-amino propionic acid or salts thereof, andN-lauryl-beta-imino-dipropionic acid or salts thereof, and mixturesthereof.

Other suitable amphoteric surfactants include those represented by theformula: ##STR3## wherein R¹ is C₈ -C₂₂ alkyl or alkenyl, preferably C₁₂-C₁₆, R² and R³ is independently selected from the group consisting ofhydrogen, CH₂ CO₂ M, CH₂ CH₂ OH, CH₂ CH₂ OCH₂ CH₂ COOM, or (CH₂ CH₂O)_(m) H wherein m is an integer from 1 to about 25, and R⁴ is hydrogen,CH₂ CH₂ OH, or CH₂ CH₂ OCH₂ CH₂ COOM, Z is CO₂ M or CH₂ CO₂ M, n is 2 or3, preferably 2, M is hydrogen or a cation, such as alkali metal (e.g.,lithium, sodium, potassium), alkaline earth metal (beryllium, magnesium,calcium, strontium, barium), or ammonium. This type of surfactant issometimes classified as an imidazoline-type amphoteric surfactant,although it should be recognized that it does not necessarily have to bederived, directly or indirectly, through an imidazoline intermediate.Suitable materials of this type are marketed under the tradename MIRANOLand are understood to comprise a complex mixture of species, and canexist in protonated and non-protonated species depending upon pH withrespect to species that can have a hydrogen at R². All such variationsand species are meant to be encompassed by the above formula.

Examples of surfactants of the above formula are monocarboxylates anddicarboxylates. Examples of these materials includecocoamphocarboxypropionate, cocoamphocarboxypropionic acid,cocoamphocarboxyglycinate (alternately referred to ascocoamphodiacetate), and cocoamphoacetate.

Commercial amphoteric surfactants include those sold under the tradenames MIRANOL C2M CONC. N. P., MIRANOL C2M CONC. O. P., MIRANOL C2M SF,MIRANOL CM SPECIAL (Miranol, Inc.); ALKATERIC 2CIB (Alkaril Chemicals);AMPHOTERGE W-2 (Lonza, Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (MonaIndustries); REWOTERIC AM-2C (Rewo Chemical Group); and SCHERCOTERICMS-2 (Scher Chemicals).

Betaine surfactants, i.e. zwitterionic surfactants, suitable for use inthe shampoo compositions are those represented by the formula: ##STR4##wherein: R₁ is a member selected from the group consisting of ##STR5##R₂ is lower alkyl or hydroxyalkyl; R₃ is lower alkyl or hydroxyalkyl;

R₄ is a member selected from the group consisting of hydrogen and loweralkyl;

R₅ is higher alkyl or alkenyl;

Y is lower alkyl, preferably methyl;

m is an integer from 2 to 7, preferably from 2 to 3;

n is the integer 1 or 0;

M is hydrogen or a cation, as previously described, such as an alkalimetal, alkaline earth metal, or ammonium. The term "lower alkyl" or"hydroxyalkyl" means straight or branch chained, saturated, aliphatichydrocarbon radicals and substituted hydrocarbon radicals having fromone to about three carbon atoms such as, for example, methyl, ethyl,propyl, isopropyl, hydroxypropyl, hydroxyethyl, and the like. The term"higher alkyl or alkenyl" means straight or branch chained saturated(i.e., "higher alkyl") and unsaturated (i.e., "higher alkenyl")aliphatic hydrocarbon radicals having from about eight to about 20carbon atoms such as, for example, lauryl, cetyl, stearyl, oleyl, andthe like. It should be understood that the term "higher alkyl oralkenyl" includes mixtures of radicals which may contain one or moreintermediate linkages such as ether or polyether linkages ornon-functional substituents such as hydroxyl or halogen radicals whereinthe radical remains of hydrophobic character.

Examples of surfactant betaines of the above formula wherein n is zerowhich are useful herein include the alkylbetaines such ascocodimethylcarboxymethylbetaine, lauryidimethylcarboxymethylbetaine,lauryl dimethyl-alpha-arboxyethylbetaine,cetyldimethyl-carboxymethylbetaine,lauryl-bis-(2-hydroxyethyl)carboxymethylbetaine,stearyl-bis-(2-hydroxypropyl)carboxymethylbetaine,oleyidimethyl-gamma-carboxypropylbetaine,lauryl-bix-(2-hydroxypropyl)alpha-carboxyethylbetaine, etc. Thesulfobetaines may be represented by cocodimethylsulfopropylbetaine,stearyidimethylsulfopropylbetaine,lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine, and the like.

Specific examples of amido betaines and amidosulfo betaines useful inthe shampoo compositions include the amidocarboxybetaines, such ascocamidodimethylcarboxymethylbetaine,laurylamidodimethylcarboxymethylbetaine,cetylamidodimethylcarboxymethylbetaine,laurylamido-bis-(2-hydroxyethyl)-carboxymethylbetaine,cocamido-bis-(2-hydroxyethyl)-carboxymethylbetaine, etc. The amidosulfobetaines may be represented by cocamidodimethylsulfopropylbetaine,stearylamidodimethylsulfopropylbetaine,laurylamido-bis-(2-hydroxyethyl)-sulfopropylbetaine, and the like.

Nonionic Surfactants

The shampoo compositions of the present invention can comprise anonionic surfactant, suitable examples of which include those compoundsproduced by condensation of alkylene oxide groups, hydrophilic innature, with an organic hydrophobic compound, which may be aliphatic oralkyl aromatic in nature.

Preferred nonlimiting examples of nonionic surfactants for use in theshampoo compositions include the following:

(1) polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to about 20 carbon atoms in either a straight chain orbranched chain configuration, with ethylene oxide, the said ethyleneoxide being resent in amounts equal to from about 10 to about 60 molesof ethylene oxide per mole of alkyl phenol;

(2) those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide and ethylenediamine products;

(3) long chain tertiary amine oxides of the formula [R¹ R² R³ N→O] whereR¹ contains an alkyl, alkenyl or monohydroxy alkyl radical of from about8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties,and from 0 to about 1 glyceryl moiety, and R² and R³ contain from about1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g.,methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals;

(4) long chain tertiary phosphine oxides of the formula [RR'R"P→O] whereR contains an alkyl, alkenyl or monohydroxyalkyl radical ranging fromabout 8 to about 18 carbon atoms in chain length, from 0 to about 10ethylene oxide moieties and from 0 to 1 glyceryl moieties and R' and R"are each alkyl or monohydroxyalkyl groups containing from about 1 toabout 3 carbon atoms;

(5) long chain dialkyl sulfoxides containing one short chain alkyl orhydroxy alkyl radical of from 1 to about 3 carbon atoms (usually methyl)and one long hydrophobic chain which include alkyl, alkenyl, hydroxyalkyl, or keto alkyl radicals containing from about 8 to about 20 carbonatoms, from 0 to about 10 ethylene oxide moieties and from 0 to 1glyceryl moieties; and

(6) alkyl polysaccharide (APS) surfactants (e.g. alkyl polyglycosides),examples of which are described in U.S. Pat. No. 4,565,647, which isincorporated herein by reference in its entirety, and which disclosesAPS surfactants having a hydrophobic group with about 6 to about 30carbon atoms and a polysaccharide (e.g., polyglycoside) as thehydrophilic group; optionally, there can be a polyalkylene-oxide groupjoining the hydrophobic and hydrophilic moieties; and the alkyl group(i.e., the hydrophobic moiety) can be saturated or unsaturated, branchedor unbranched, and unsubstituted or substituted (e.g., with hydroxy orcyclic rings); a preferred material is alkyl polyglucoside which iscommercially available from Henkel, ICI Americas, and Seppic.

The preferred shampoo compositions of the present invention comprisefrom about 5.0% to about 50% of a detersive surfactant componentcomprising: i) an ethoxylated alkyl sulfate surfactant having from about1 to about 8 moles of ethoxylation; and ii) an amphoteric surfactantcomponent to provide cleaning performance to the composition and whereinsaid the resulting composition comprises less than about 5%, preferablyless than about 3% and most preferably less than about 2% of alkylsulfate ethoxylated surfactant having less than 1 mole of ethoxylation.

Insoluble Hair Conditioning Component

The shampoo compositions of the present invention further comprises aninsoluble hair conditioning component having a mean particle size ofless than about 0.15 microns.

The hair conditioning component is used at concentrations effective toprovide hair conditioning benefits. Such concentrations generally rangefrom about 0.005% to about 10%, preferably from about 0.05% to about 5%,more preferably from about 0.1% to about 4%, most preferably from about0.2% to about 3%, by weight of the shampoo compositions. Thenon-volatile conditioning agent in the present invention has a meanparticle size range below about 0.15 microns, preferably below about 0.1microns, more preferably below about 0.05 microns, and preferablygreater than about 0.01 microns.

As used herein, average particle size of the conditioning agentparticles may be measured within the shampoo compositions by lightscattering methods well known in the art for determining averageparticle size for emulsified liquids. One such method involves the useof a Horiba LA-910 particle size analyzer.

The particle size range materials can be formed by mechanicalemulsification or by emulsion polymerization, both means are well-knownin the art, see, for example, U.S. Pat. No. 4,733,677, issued Mar. 29,1988 to Gee et al., and U.S. Pat. No. 5,085,857 issued Feb. 4, 1992 toReid et al. and WO 95/09599, published Apr. 13, 1995 to Murray, all ofwhich are incorporated by reference herein. When forming a highlyviscous conditioning component, emulsion polymerization is the preferredmethod of manufacturing the emulsion.

The particles can be the same material, different materials, or mixturesof different materials as described below. Useful conditioning agentsinclude, but are not limited to non-volatile silicone conditioningagents, hydrocarbon oils, fatty ester oils and petrolatum, preferablysilicone and are described in detail below.

Silicone Hair Conditioning Agent

Most preferred for use herein are non-volatile silicone conditioningagents. Typically it will be intermixed in the shampoo composition so asto be in the form of a separate, discontinuous phase of dispersed,insoluble particles, also referred to as droplets. These droplets may besuspended with a suspending agent described hereinafter. The siliconehair conditioning agent phase will comprise a silicone fluid hairconditioning agent such as a silicone fluid and can also comprise otheringredients, such as silicone gums and resins to enhance silicone fluiddeposition efficiency or enhance glossiness of the hair (especially whenhigh refractive index (e.g. above about 1.46) silicone conditioningagents are used (e.g. highly phenylated silicones).

As used herein, "nonvolatile" refers to silicone material with little orno significant vapor pressure under ambient conditions, as is understoodby those in the art. Boiling point under one atmosphere (atm) willpreferably be at least about 250° C., more preferably at least about275° C., most preferably at least about 300° C. Vapor pressure ispreferably about 0.2 mm HG at 25° C. or less, preferably about 0.1 mm HGat 25° C. or less.

The silicone hair conditioning agent phase may comprise volatilesilicone, nonvolatile silicone, or mixtures thereof. Typically, ifvolatile silicones are present, it will be incidental to their use as asolvent or carrier for commercially available forms of nonvolatilesilicone materials ingredients, such as silicone gums and resins.

The silicone hair conditioning agents for use in the shampoocompositions preferably have a viscosity of from about 20 to about2,000,000 centistokes, more preferably from about 1,000 to about1,500,000 centistokes, most preferably from about 10,000 to about1,000,000 centistokes, at 25° C. The viscosity can be measured by meansof a glass capillary viscometer as set forth in Dow Corning CorporateTest Method CTM0004, Jul. 20, 1970.

Other silicone hair conditioning agents for use in the shampoocompositions includes silicone oil which are flowable silicone materialswith a viscosity of less than 1,000,000 centistokes, preferably betweenabout 5 and 1,000,000 centistokes, more preferably between about 10 andabout 600,000 centistokes, more preferably between about 10 and about500,000 centistokes, most preferably between 10 and 300,000 centistokesat 25° C. Suitable silicone oils include polyalkyl siloxanes, polyarylsiloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, andmixtures thereof. Other insoluble, nonvolatile silicone fluids havinghair conditioning properties can also be used.

Optional Silicone oils for use in the composition include polyalkyl orpolyaryl siloxanes which conform to following formula: ##STR6## where Ris aliphatic, preferably alkyl or alkenyl, or aryl, R can be substitutedor unsubstituted, and x is an integer from 1 to about 8,000. Suitableunsubstituted R groups include alkoxy, aryloxy, alkaryl, arylalkyl,arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, andhalogen-substituted aliphatic and aryl groups. Suitable R groups alsoinclude cationic amines and quaternary ammonium groups.

The aliphatic or aryl groups substituted on the siloxane chain may haveany structure as long as the resulting silicones remain fluid at roomtemperature, are hydrophobic, are neither irritating, toxic norotherwise harmful when applied to the hair, are compatible with theother components of the shampoo compositions, are chemically stableunder normal use and storage conditions, are insoluble in the shampoocompositions, and are capable of being deposited on and, ofconditioning, the hair.

The two R groups on the silicon atom of each monomeric silicone unit mayrepresent the same group or different groups. Preferably, the two Rgroups represent the same group.

Preferred alkyl and alkenyl substituents are C₁ -C₅ alkyls and alkenyls,more preferably from C₁ -C₄, most preferably from C₁ -C₂. The aliphaticportions of other alkyl-, alkenyl-, or alkynyl-containing groups (suchas alkoxy, alkaryl, and alkamino) can be straight or branched chains andpreferably have from one to five carbon atoms, more preferably from oneto four carbon atoms, even more preferably from one to three carbonatoms, most preferably from one to two carbon atoms. As discussed above,the R substituents hereof can also contain amino functionalities, e.g.alkamino groups, which can be primary, secondary or tertiary amines orquaternary ammonium. These include mono-, di- and tri-alkylamino andalkoxyamino groups wherein the aliphatic portion chain length ispreferably as described above. The R substituents can also besubstituted with other groups, such as halogens (e.g. chloride,fluoride, and bromide), halogenated aliphatic or aryl groups, andhydroxy (e.g. hydroxy substituted aliphatic groups). Suitablehalogenated R groups could include, for example, tri-halogenated(preferably fluoro) alkyl groups such as --R¹ --C(F)₃, wherein R¹ is C₁-C₃ alkyl. Examples of such polysiloxanes includepolymethyl-3,3,3trifluoropropylsiloxane.

Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyland phenylmethyl. The preferred silicones are polydimethyl siloxane,polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxaneis especially preferred. Other suitable R groups include methyl,methoxy, ethoxy, propoxy, and aryloxy. The three R groups on the endcaps of the silicone may also represent the same or different groups.

The nonvolatile polyalkylsiloxane fluids that may be used include, forexample, polydimethylsiloxanes. These siloxanes are available, forexample, from the General Electric Company in their Viscasil R and SF 96series, and from Dow Corning in their Dow Corning 200 series.

The polyalkylaryl siloxane fluids that may be used, also include, forexample, polymethylphenylsiloxanes. These siloxanes are available, forexample, from the General Electric Company as SF 1075 methyl phenylfluid or from Dow Corning as 556 Cosmetic Grade Fluid.

The polyether siloxane copolymers that may be used include, for example,a polypropylene oxide modified polydimethylsiloxane (e.g., Dow CorningDC-1248) although ethylene oxide or mixtures of ethylene oxide andpropylene oxide may also be used. The ethylene oxide and polypropyleneoxide level must be sufficiently low to prevent solubility in water andthe composition hereof.

Suitable alkylamino substituted silicones include those conforming tothe following formula: ##STR7## wherein x and y are integers. Thispolymer is also known as "amodimethicone".

Suitable cationic silicone fluids include those conforming to theformula described hereinabove, wherein (R₁)_(a) G_(3-a)--Si--(--OSiG₂)_(n) -(--OSiG_(b) (R₁)_(2-b))_(m) --O--SiG_(3-a) (R₁)_(a)in which G is chosen from the group consisting of hydrogen, phenyl, OH,C₁ -C₈ alkyl and preferably methyl; a denotes 0 or an integer from 1 to3, and preferably equals 0; b denotes 0 or 1 and preferably equals 1;the sum n+m is a number from 1 to 2,000 and preferably from 50 to 150, nbeing able to denote a number from 0 to 1,999 and preferably from 49 to149 and m being able to denote an integer from 1 to 2,000 and preferablyfrom 1 to 10; R₁ is a monovalent radical of formula CqH_(2q) L in whichq is an integer from 2 to 8 and L is chosen from the groups

    --N(R.sub.2)CH.sub.2 --CH.sub.2 --N(R.sub.2).sub.2

    --N(R.sub.2).sub.2

    --N(R.sub.2).sub.3 A.sup.-

    --N(R.sub.2)CH.sub.2 --CH.sub.2 --NR.sub.2 H.sub.2 A.sup.-

in which R₂ is chosen from the group consisting of hydrogen, phenyl,benzyl, a saturated hydrocarbon radical, preferably an alkyl radicalcontaining from 1 to 20 carbon atoms, and A⁻ denotes a halide ion.

An especially preferred cationic silicone corresponding to the previousformula is the polymer known as "trimethylsilylamodimethicone", whichconforms to the following formula: ##STR8##

Other silicone cationic polymers which can be used in the shampoocompositions are those which conform to the following formula: ##STR9##where R³ denotes a monovalent hydrocarbon radical having from 1 to 18carbon atoms, preferably an alkyl or alkenyl radical such as methyl; R₄denotes a hydrocarbon radical, preferably a C₁ -C₁ alkylene radical or aC₁ -C₁₈, and more preferably C₁ -C₈, alkyleneoxy radical; Q⁻ is a halideion, preferably chloride; r denotes an average statistical value from 2to 20, preferably from 2 to 8; s denotes an average statistical valuefrom 20 to 200, and preferably from 20 to 50. A preferred polymer ofthis class is available from Union Carbide under the name "UCAR SILICONEALE 56."

Other suitable silicone fluids for use in the silicone conditioningagents are insoluble silicone gums. These gums are polyorganosiloxanematerials having a viscosity at 25° C. of greater than or equal to1,000,000 centistokes. Silicone gums are described in U.S. Pat. No.4,152,416; Noll and Walter, Chemistry and Technology of Silicones, NewYork: Academic Press 1968; and in General Electric Silicone RubberProduct Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which areincorporated herein by reference. The silicone gums will typically havea mass molecular weight in excess of about 200,000, generally betweenabout 200,000 and about 1,000,000, specific examples of which includepolydimethylsiloxane, (polydimethylsiloxane) (methylvinylsiloxane)copolymer, poly(dimethylsiloxane) (diphenylsiloxane)(methylvinylsiloxane) copolymer and mixtures thereof.

The silicone hair conditioning agent can also comprise a mixture ofpolydimethylsiloxane gum (viscosity greater than about 1,000,000centistokes) and polydimethylsiloxane oil (viscosity from about 10 toabout 100,000 centistokes).

Another category of nonvolatile, insoluble silicone fluid conditioningagents are high refractive index silicones, having a refractive index ofat least about 1.46, preferably at least about 1.48, more preferably atleast about 1.52, most preferably at least about 1.55. Although notintended to necessarily be limiting, the refractive index of thepolysiloxane fluid will generally be less than about 1.70, typicallyless than about 1.60. Polysiloxane "fluid" includes oils as well asgums.

The high refractive index polysiloxane fluid suitable for purposeshereof includes those conforming to the formula described hereinabove,as well as cyclic polysiloxanes such as those conforming to thefollowing formula: ##STR10## wherein R is as defined above, n is fromabout 3 to about 7, preferably from 3 to 5.

The high refractive index polysiloxane fluids contain a sufficientamount of aryl-containing R substituents to increase the refractiveindex to the desired level, which is described above. In addition, R andn must be selected so that the material is nonvolatile, as definedabove.

Aryl-containing substituents contain alicyclic and heterocyclic five andsix membered aryl rings, and substituents containing fused five or sixmembered rings. The aryl rings themselves can be substituted orunsubstituted. Substituents include aliphatic substituents, and can alsoinclude alkoxy substituents, acyl substituents, ketones, halogens (e.g.,Cl and Br), amines, etc. Exemplary aryl-containing groups includesubstituted and unsubstituted arenes, such as phenyl, and phenylderivatives such as phenyls with C₁ -C₅ alkyl or alkenyl substituents,e.g., allylphenyl, methyl phenyl and ethyl phenyl, vinyl phenyls such asstyrenyl, and phenyl alkynes (e.g. phenyl C₂ -C₄ alkynes). Heterocyclicaryl groups include substituents derived from furan, imidazole, pyrrole,pyridine, etc. Fused aryl ring substituents include, for example,napthalene, coumarin, and purine.

In general, the high refractive index polysiloxane fluids will have adegree of aryl-containing substituents of at least about 15%, preferablyat least about 20%, more preferably at least about 25%, even morepreferably at least about 35%, most preferably at least about 50%.Typically, although it is not intended to necessarily limit theinvention, the degree of aryl substitution will be less than about 90%,more generally less than about 85%, preferably from about 55% to about80%.

The polysiloxane fluids are also characterized by relatively highsurface tensions as a result of their aryl substitution. In general, thepolysiloxane fluids hereof will have a surface tension of at least about24 dynes/cm², typically at least about 27 dynes/cm². Surface tension,for purposes hereof, is measured by a de Nouy ring tensiometer accordingto Dow Corning Corporate Test Method CTM 0461, Nov. 23, 1971. Changes insurface tension can be measured according to the above test method oraccording to ASTM Method D 1331.

Preferred high refractive index polysiloxane fluids have a combinationof phenyl or phenyl derivative substituents (preferably phenyl), withalkyl substituents, preferably C₁ -C₄ alkyl (most preferably methyl),hydroxy, C₁ -C₄ alkylamino (especially --R¹ NHR² NH² where each R¹ andR² independently is a C₁ -C₃ alkyl, alkenyl, and/or alkoxy. Highrefractive index polysiloxanes are available from Dow CorningCorporation (Midland, Mich., U.S.A.) Huls America (Piscataway, N.J.,U.S.A.), and General Electric Silicones (Waterford, N.Y., U.S.A.).

References disclosing examples of some suitable silicone fluids for usein the shampoo compositions include U.S. Pat. No. 2,826,551, U.S. Pat.No. 3,964,500, U.S. Pat. No. 4,364,837, British Patent 849,433, andSilicon Compounds. Petrarch Systems, Inc. (1984), all of which areincorporated herein by reference.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, can befound in Encyclopedia of Polymer Science and 5 Engineering, Volume 15,Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989, incorporatedherein by reference.

Crystalline Agents

The shampoo compositions of the present invention further comprises acrystalline agent. Without being limited by theory, Applicants believethat these agents provide improved wet feel as well as may provide asuspending benefit for the conditioning agents such as the preferredsilicone conditioning agent, or other water-insoluble material, indispersed form in the shampoo compositions. Such concentrations rangefrom about 0.1% to about 10%, preferably from about 0.3% to about 5.0%,and most preferably from about 0.5% to about 3.0%, by weight of theshampoo compositions. These agent preferably have a mean particle sizeranging from about 0.1 microns to about 5 microns, preferably from about0.1 microns to about 2 microns, and most preferably from about 0.2microns to about 1 microns.

Crystalline agents include those which can be categorized as acylderivatives, long chain amine oxides, and mixtures thereof. These agentsare described in U.S. Pat. No. 4,741,855, which description isincorporated herein by reference. These preferred agents include mono-and di-ethylene glycol esters of fatty acids preferably having fromabout 16 to about 22 carbon atoms. More preferred are the ethyleneglycol stearates, both mono and distearate, but particularly thedistearate containing less than about 7% of the mono stearate. Othersuitable agents include alkanol amides of fatty acids, preferably havingfrom about 16 to about 22 carbon atoms, more preferably about 16 to 18carbon atoms, preferred examples of which include stearicmonoethanolamide, stearic diethanolamide, stearic monoisopropanolamideand stearic monoethanolamide stearate. Other long chain acyl derivativesinclude long chain esters of long chain fatty acids (e.g., stearylstearate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryldistearate) and long chain esters of long chain alkanol amides (e.g.,stearamide diethanolamide distearate, stearamide monoethanolamidestearate). Long chain acyl derivatives, ethylene glycol esters of longchain carboxylic acids, long chain amine oxides, and alkanol amides oflong chain carboxylic acids in addition to the preferred materialslisted above may be used as suspending agents. For example, it iscontemplated that suspending agents with long chain hydrocarbyls havingC₈ -C₂₂ chains may be used.

Other long chain acyl derivatives suitable for use herein includeN,N-dihydrocarbyl amido benzoic acid and soluble salts thereof (e.g.,Na, K), particularly N,N-di(hydrogenated) C ₁₆, C₁₈ and tallow amidobenzoic acid species of this family, which are commercially availablefrom Stepan Company (Northfield, Ill., USA).

Examples of suitable long chain amine oxides for use herein includealkyl (C₁₆ -C₂₂) dimethyl amine oxides, e.g., stearyl dimethyl amineoxide.

Other suitable agents include primary amines having a fatty alkyl moietyhaving at least about 16 carbon atoms, examples of which includepalmitamine or stearamine, and secondary amines having two fatty alkylmoieties each having at least about 12 carbon atoms, examples of whichinclude dipalmitoylamine or di(hydrogenated tallow)amine. Still othersuitable agents include di(hydrogenated tallow)phthalic acid amide.

Deposition Polymer

A deposition polymer is an essential element of the present invention.Without being limited by theory, Applicants believe that the depositionpolymer ensures deposition of the conditioning agent having a meanparticle range of less than about 0.15 microns. It will generally bepresent at levels of from 0.01 to 5%, preferably from about 0.05 to 1%,more preferably from about 0.08% to about 0.5% by weight. The polymermay be a homopolymer or be formed from two or more types of monomers.The molecular weight of the polymer will generally be between about5,000 and about 20,000,000, preferably between about 50,000 and about5,000,000, and most preferably in the range between about 100,000 toabout 2,000,000.

Preferably the deposition polymer is a cationic polymer and preferablywill have cationic nitrogen containing groups, or a mixture thereof. Thecationic charge density has been found to need to be at least about 0.1meq/g, preferably above about 0.5 and most preferably above about 0.8 orhigher. The cationic charge density should not exceed about 5 meq/g, itis preferably less than about 3 and more preferably less than about 2meq/g. The charge density can be measured using the Kjeldahl method andshould be within the above limits at the desired pH of use, which willin general be from about 3 to 9 and preferably between 4 and 8.

The cationic nitrogen-containing group will generally be present as asubstituent on a fraction of the total monomer units of the cationicpolymer. Thus when the cationic polymer is not a homopolymer it cancontain spacer non-cationic monomer units. Such polymers are describedin the CTFA Cosmetic Ingredient Directory, 3rd edition.

Suitable cationic polymers include, for example, copolymers of vinylmonomers having cationic amine or quaternary ammonium functionalitieswith water soluble spacer monomers such as (meth)acrylamide, alkyl anddialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone andvinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferablyhave C1-C7 alkyl groups, more preferably C1-C3 alkyl groups. Othersuitable spacers include vinyl esters, vinyl alcohol, maleic anhydride,propylene glycol and ethylene glycol.

The cationic amines can be primary, secondary or tertiary amines,depending upon the particular species and the pH of the shampoo. Ingeneral secondary and tertiary amines, especially tertiary, arepreferred.

Amines substituted vinyl monomers and amines can be polymerized in theamine form and then converted to ammonium by quaternization.

Suitable cationic amino and quaternary ammonium monomers include, forexample, vinyl compounds substituted with dialkyl aminoalkyl acrylate,dialkylamino alkylmethacrylate, monoalkylaminoalkyl acrylate,monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammoniumsalt, trialkyl acryloxyalkyl ammonium sale, diallyl quaternary ammoniumsalts, and vinyl quaternary ammonium monomers having cyclic cationicnitrogen-containing rings such as pyridinium, imidazolium, andquaternized pyrrolidine, e.g., alkyl vinyl imidazolium, and quaternizedpyrrolidine, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium,alkyl vinyl pyrrolidine salts. The alkyl portions of these monomers arepreferably lower alkyls such as the C₁ -C₃ alkyls, more preferably C₁and C₂ alkyls.

Suitable amine-substituted vinyl monomers for use herein includedialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate,dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide,wherein the alkyl groups are preferably C₁ -C₇ hydrocarbyls, morepreferably C₁ -C₃ alkyls.

The cationic polymers hereof can comprise mixtures of monomer unitsderived from amine- and/or quaternary ammonium-substituted monomerand/or compatible spacer monomers.

Suitable cationic hair conditioning polymers include, for example:copolymers of 1-vinyl-2-pyrrolidine and 1-vinyl-3-methyl-imidazoliumsalt (e.g., Chloride salt) (referred to in the industry by the Cosmetic,Toiletry, and Fragrance Association, "CTFA" as Polyquaternium-16) suchas those commercially available from BASF Wyandotte Corp. (Parsippany,N.J., USA) under the LUVIQUAT tradename (e.g., LUVIQUAT FC 370);copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate(referred to in the industry by CTFA and Polyquaternium-11) such asthose commercially from ISP Corporation (Wayne, N.J., USA) under theGAFQUAT tradename (e.g., GAFQAT 755N); cationic diallyl quaternaryammonium-containing polymers including, for example,dimethyidiallyammonium chloride homopolymer and copolymers of acrylamideand dimethyidiallyammonium chloride, referred to in the industry (CTFA)as Polyquaternium 6 and Polyquaternium 7, respectively; and mineral acidsalts of amino-alkyl esters of homo-and co-polymers of unsaturatedcarboxylic acids having from 3 to 5 carbon atoms, as described in U.S.Pat. No. 4,009,256, incorporated herein by reference.

Other cationic polymers that can be used include polysaccharidepolymers, such as cationic cellulose derivatives and cationic starchderivatives. Cationic polysaccharide polymer materials suitable for useherein include those of the formula: ##STR11## wherein: A is ananhydroglucose residual group, such as starch or celluloseanhydroglucose residual, R is an alkylene oxyalklene, polyoxyalkylene,or hydroxyalkylene group, or combination thereof, R¹, R² and R³independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, oralkoxyaryl groups, each group containing up to about 18 carbon atoms,and the total number of carbon atoms for each cationic moiety (i.e., thesum of carbon atoms in R¹, R² and R³) preferably being about 20 or less,and X is an anionic counterion, as previously described.

Cationic cellulose is available from Amerchol Corp. (Edison, N.J., USA)in their Polymer JR (trademark) and LR (trade mark) series of polymers,as salts of hydroxyethyl cellulose reacted with trimethyl ammoniumsubstituted epoxide, referred to in the industry (CTFA) asPolyquaternium 10. Another type of cationic cellulose includes thepolymeric quaternary ammonium salts of hydroxyethyl cellulose reactedwith lauryl dimethyl ammonium-substituted epoxide, referred to in theindustry (CTFA) as Polyquaternium 24. These materials are available fromAmerchol Corp. (Edison, N.J., USA) under the tradename Polymer LM-200.

Other cationic polymers that can be used include cationic guar gumderivatives, such as guar hydroxypropyltrimonium chloride (commerciallyavailable from Celanese Corp. in their Jaguar trade mark series). Othermaterials include quaternary nitrogen-containing cellulose ethers (e.g.,as described in U.S. Pat. No. 3,962,418, incorporated by referenceherein), and copolymers of etherified cellulose and starch (e.g., asdescribed in U.S. Pat. No. 3,958,581, incorporated by reference herein).

The deposition polymer does not have to be soluble in the shampoocomposition. Preferably, however, the cationic polymer is either solublein the shampoo composition, or in a complex coacervate phase in theshampoo composition formed by the cationic polymer and anionic material.Complex coacervates of the cationic polymer can be formed with anionicsurfactants or with anionic polymers that can optionally be added to thecomposition hereof (e.g., sodium polystyrene sulfonate).

Coacervate formation is dependent upon a variety of criteria such asmolecular weight, concentration, and ratio of interacting ionicmaterials, ionic strength (including modification of ionic strength, forexample, by addition of salts), charge density of the cationic andanionic species, pH, and temperature. Coacervate systems and the effectof these parameters have been described, for 30 example, by J. Caelles,et al., "Anionic and Cationic Compounds in Mixed Systems", Cosmetics &Toiletries, Vol. 106, April 1991, pp 49-54, C. J. van Oss,"Coacervation, Complex-Coacervation and Flocculation", J DispersionScience and Technology, Vol. 9 (5,6), 1988-89, pp 561-573, and D. J.Burgess, "Practical Analysis of Complex Coacervate Systems", J ofColloid and Interface Science, Vol. 140, No. 1, November 1990, pp227-238, which descriptions are incorporated herein by reference.

It is believed to be particularly advantageous for the cationic polymerto be present in the shampoo in a coacervate phase, or to form acoacervate phase upon application or rinsing of the shampoo to or fromthe hair. Complex coacervates are believed to more readily deposit onthe hair. Thus, in general, it is preferred that the cationic polymerexist in the shampoo as a coacervate phase or form a coacervate phaseupon dilution. If not already a coacervate in the shampoo, the cationicpolymer will preferably exist in a complex coacervate form in theshampoo upon dilution with water to a water:shampoo composition rateratio of about 20:1, more preferably at about 10:1, even more preferablyat about 8:1.

Techniques for analysis of formation of complex coacervates are known inthe art. For example, microscopic analyses of the shampoo compositions,at any chosen stage of dilution, can be utilized to identify whether acoacervate phase has formed. Such coacervate phase will be identifiableas an additional emulsified phase in the composition. The use of dyescan aid in distinguishing the coacervate phase from other insolublephase dispersed in the composition.

Preferably the deposition polymer is selected from the group comprisinghydroxyalkyl cellulose ethers and cationic guar derivatives.Particularly preferred deposition polymers are Jaguar C13S, Jaguar C15,Jaguar C17 and Jaguar C16 and Jaguar C162. Preferred cellulose ethersinclude Polymer JR400, JR30M and JR 125.

Water

The shampoo compositions of the present invention comprise from about20% to about 94%, preferably from about 50% to about 94%, morepreferably from about 60% to about 85%, by weight of water.

Other Optional Components

The shampoo compositions of the present invention may further compriseone or more optional components known for use in shampoo or conditioningcompositions, provided that the optional components are physically andchemically compatible with the essential component described herein, ordo not otherwise unduly impair product stability, aesthetics orperformance. Concentrations of such optional components typically rangefrom about 0.001% to about 10% by weight of the shampoo compositions.

Optional components include anti static agents, dyes, organic solventsor diluents, pearlescent aids, foam boosters, additional surfactants orcosurfactants (nonionic, cationic, zwitterionic), pediculocides, pHadjusting agents, perfumes, preservatives, proteins, skin active agents,suspending agents, styling polymers, sunscreens, thickeners, vitamins,and viscosity adjusting agents. This list of optional components is notmeant to be exclusive, and other optional components can be used.

Method of Manufacture

The shampoo compositions of the present invention can be prepared byusing various formulation and mixing techniques or methods known in theart for preparing surfactant or conditioning compositions, or othersimilar compositions.

Method of Use

The shampoo compositions of the present invention are used in aconventional manner for cleansing and conditioning hair or skin. Aneffective amount of the composition for cleansing and conditioning thehair or skin is applied to the hair or skin, that has preferably beenwetted with water, and then rinsed off. Such effective amounts generallyrange from about 1 g to about 50 g, preferably from about 1 g to about20 g. Application to the hair typically includes working the compositionthrough the hair such that most or all of the hair is contacted with thecomposition.

This method for cleansing and conditioning the hair comprises the stepsof: a) wetting the hair with water, b) applying an effective amount ofthe shampoo composition to the hair, and c) rinsing the shampoocomposition from the hair using water. These steps can be repeated asmany times as desired to achieve the desired cleansing and conditioningbenefit.

EXAMPLES

The shampoo compositions illustrated in Examples I-X illustrate specificembodiments of the shampoo compositions of the present invention, butare not intended to be limiting thereof. Other modifications can beundertaken by the skilled artisan without departing from the spirit andscope of this invention. These exemplified embodiments of the shampoocompositions of the present invention provide cleansing of hair andimproved hair conditioning performance.

The compositions are prepared as follows.

For Examples I-X, about one-third to all of the total alkyl sulfatesurfactant (ammonium laureth-3 sulfate (added as a 25% solution) and/orammonium lauryl sulfate (added as a 25% solution)) is added to ajacketed mix tank and heated to about 74° C. with slow agitation to forma surfactant solution. Cocamide MEA and fatty alcohol, as applicable,are added to the tank and allowed to disperse. Ethylene glycoldistearate (EGDS) is then added to the mixing vessel, and melted. Afterthe EGDS is well dispersed (usually about 5 to 20 minutes) polyethyleneglycol and the preservative, if used are added and mixed into thesurfactant solution. This mixture is passed through a heat exchangerwhere it is cooled to about 35° C. and collected in a finishing tank. Asa result of this cooling step, the ethylene glycol distearatecrystallizes to form a crystalline network in the product. The remainderof the ammonium laureth sulfate, lauryl sulfate and other ingredientsincluding the silicone emulsions are added to the finishing tank withample agitation to insure a homogeneous mixture. A sufficient amount ofthe silicone emulsion is added to provide the desired level ofdimethicone in the final product. The non-silicone polymers aretypically dispersed in water as a 1% to 10% solution before addition tothe final mix. Once all ingredients have been added, ammonium xylenesulfonate or additional sodium chloride can be added to the mixture tothin or thicken respectively to achieve a desired product viscosity.Preferred viscosities range from about 3500 to about 9000 cS at 25° C.(as measured by a Wells-Brookfield cone and plate viscometer at 15/s).

The compositions of the Examples can provide excellent in-use haircleaning, lather, mildness, dandruff control (where applicable), andespecially wet conditioning and conditioning impression.

    ______________________________________                                                     Example Number                                                   Component      I       II     III   IV   V                                    ______________________________________                                        Ammonium Laureth-3 Sulfate                                                                   14.00   14.00  14.0  14.85                                                                              12.50                                Cocamidopropylbetaine                                                                        2.70    2.70   2.70  1.85 4.20                                 Polyquaternium-10 (3)                                                                        0.15    0.15   0.10  0.15 0.15                                 Cocamide MEA   0.80    0.80   0.80  0.80 0                                    Cetyl Alcohol  0.42    0.42   0.42  0.42 0                                    Stearyl Alcohol                                                                              0.18    0.18   0.18  0.18 0                                    Ethylene Glycol Distearate                                                                   1.50    1.50   0.75  1.50 0.75                                 Dimethicone (1)                                                                              0.5     0.3    0.5   0.3  0.5                                  Perfume Solution                                                                             0.70    0.70   0.70  0.70 0.70                                 DMDM Hydantoin 0.37    0.37   0.37  0.37 0.37                                 Color Solution (ppm)                                                                         64      64     64    64   64                                   Water and Minors                                                                             q.s. to 100%                                                   ______________________________________                                                     Example Number                                                   Component      VI      VII    VIII  IX   X                                    ______________________________________                                        Ammonium Laureth-3 Sulfate                                                                   14.00   14.00  14.00 10.00                                                                              10.00                                Cocamidopropylbetaine                                                                        2.70    2.70   2.70  2.00 2.00                                 Polyquaternium-10 (3)                                                                        0.15    0.15   0.15  0.10 0.10                                 Cocamide MEA   0.80    0.80   0     0.80 0.60                                 Cetyl Alcohol  0.42    0.42   0     0.42 0                                    Stearyl Alcohol                                                                              0.18    0.18   0     0.18 0                                    Ethylene Glycol Distearate                                                                   1.50    1.50   1.0   1.50 1.0                                  Dimethicone (2)                                                                              0.5     0.3    1.0   0.75 0.20                                 Perfume Solution                                                                             0.70    0.70   0.70  0.70 0.70                                 DMDM Hydantoin 0.37    0.37   0.37  0.37 0.37                                 Color Solution (ppm)                                                                         64      64     64    64   64                                   Water and Minors                                                                             q.s. to 100%                                                   ______________________________________                                         (1) Dimethicone is an emulsion of 125,000 csk polydimethyl siloxane with      particle size of approximately 50 nm available from Dow Corning (21550;       1330592).                                                                     (2) Dimethicone is an emulsion of 350,000 csk polydimethyl siloxane with      particle size of approximately 45 nm available from Dow Corning (21550;       1370938).                                                                     (3) Polyquaternium10 is JR30M, a cationic cellulose derived polymer           available from Amerchol.                                                 

What is claimed is:
 1. An aqueous shampoo composition comprising:a) fromabout 5.0% to about 50% of an alkyl ether sulfate surfactant componentconforming to the general formula:

    RO(C.sub.2 H.sub.4 O).sub.x SO.sub.3 M

wherein R is a C₈ to C₃₀ alkyl, x is 1 to 10 and M is selected from thegroup consisting of hydrogen, cation, monovalent metal cation, andpolyvalent metal cation; b) a non-volatile conditioning agent having amean particle size of less than about 0.15 microns, wherein saidnon-volatile conditioning agent is either polyalkyl or polyaryl siloxaneconforming to the general formula: ##STR12## wherein R is aliphatic andis substituted or unsubstituted, and x is an integer from 1 to about8,000; c) from about 0.01% to about 3.0% of a deposition polymer; d)from about 0.1% to about 5% of a crystalline agent, wherein saidcrystalline agent is an ethylene glycol ester of a fatty acid havingfrom 16 to 22 carbon atoms; and e) an aqueous carrier.
 2. An aqueousshampoo composition according to claim 1 which comprises from about 8.0%to about 30% of said alkyl ether sulfate surfactant component andwherein said non-volatile conditioning agent has a mean particle size ofless than about 0.1 microns.
 3. An aqueous shampoo composition accordingto claim 2 wherein said non-volatile conditioning agent has a meanparticle size range of from about 0.01 to about 0.1 microns.
 4. Anaqueous shampoo composition according to claim 3 wherein saidnon-volatile conditioning agent has a mean particle size range of fromabout 0.01 to about 0.05 microns.
 5. An aqueous shampoo compositionaccording to claim 3 wherein said non-volatile silicone conditioningagent is polydimethylsiloxane.
 6. An aqueous shampoo compositionaccording to claim 5 wherein said an alkyl ether surfactant componentcomprises: i) an ethoxylated alkyl sulfate surfactant having from about1 to about 8 moles of ethoxylation; and ii) an amphoteric surfactantwherein said composition comprises less than about 5% of ethoxylatedalkyl sulfate surfactant having less than 1 mole of ethoxylation andwherein said deposition polymer is a cationic cellulosic polymer hairconditioning agent has a cationic charge density of from about 0.7meq/gram.
 7. An aqueous shampoo composition according to claim 6 whereinsaid composition comprises an additional anionic surfactant and whereinsaid composition comprises less than about 2% of ethoxylated surfactanthaving less than 1 mole of ethoxylation.
 8. An aqueous shampoocomposition according to claim 7 wherein said cationic cellulosicpolymer hair conditioning agent is Polyquaternium-10.
 9. An aqueousshampoo composition according to claim 8 wherein said cationiccellulosic polymer hair conditioning agent has a cationic charge densityof from about 0.9 meq/gram to about 1.5 meq/gram.
 10. An aqueous shampoocomposition according to claim 9 wherein said amphoteric surfactant iscocoamidopropyl betaine and comprises from about 1% to about 10% of thecomposition.
 11. An aqueous shampoo composition according to claim 10wherein said amphoteric surfactant is cocoamidopropyl betaine andcomprises from about 2% to about 5% of the composition.
 12. An aqueousshampoo composition according to claim 11 wherein said non volatilesilicone conditioning agent comprises from about 0.05% to about 4% ofthe composition.
 13. An aqueous shampoo composition according to claim12 wherein said non-volatile silicone conditioning agent comprises fromabout 0.2% to about 3% of the composition.
 14. A method for providingimproved wet feel to hair by shampooing the hair in a compositionaccording to claim 1.